Methylenebis [(nu-hydroxyalkyl-piperidyl) alkyl] piperidines



EXAivllNER 3,352,875 Patented Nov. 14, 1967 "ice of formaldehyde in water is added over a ten-minute 3,352,875 period. As the last of the formaldehyde solution is added,

METHYLENEBIS[(N-HYDROXYALKYL-PIPERI- DYL) ALKYL] PIPERIDINES Charles K. McGill, Indianapolis, Ind., assignor to Reilly Tar & Chemical Corporation, Indianapolis, Ind., a corporation of Indiana No Drawing. Filed July 28, 1965, Ser. No. 475,577

Claims. (Cl. 260-294.

This invention relates to new compositions of matter. More particularly, it relates to a group of new organic compounds having the structure Some of my new compounds may be prepared by re- 2 acting formaldehyde with an N-hydroxyalkylpiperidyl, piperidyl alkane; others may be prepared by reacting an the product, i.e. 1,1'-methylenebis 4-[3-(N-beta-hydroxyethyl-4-piperidyl)propyl] piperidine begins to separate from the solution. The temperature of the mixture is now raised to about 45 C., product to re-dissolve. The resulting solution is stirred at 45 C. for about two hours. Then the solution is cooled to about -25 C., and the resulting solids are separated by filtration and dried.

The dried product has a melting point of about 116- 119 C.

Example 2.1,1'-methylenebis Z-[Z-(N-beta-hydroxyethyl-2-piperidyl) ethyl] piperidine S S CHaCH N N N-hydroxyalkylpiperidyl, piperidyl alkane with a poly- H1 methylene dihalide in the presence of an alkali metal 5 hydroxide or carbonate. H 2

The methylenebis[ (N hydroxyalkyl piperidyl)alkyl] piperidines of my invention are (ii-functional alcohols. They have the chemical properties associated with alcohols and are capable of entering into the same type of reactions as other ditunctional alcohols, within the limits imposed by the piperidine nucleus. They are non-volatile and are insoluble in water. They are somewhat soluble in organic solvents such, for example, as benzene.

Some of my methylenebis [(N-hydroxyalkyl-piperidyl) alkyl] piperidines are primary alcohols. They are also tertiary amines. These tertiary amines, with their two primary alcohol groups, can function as a catalyst and chain extender in polyurethane foams.

The methylenebis[(N hydroxyalkyl piperidyl)alkyl] piperidines are useful as rust preventive coatings. They are also useful as plasticizers in conjunction with polyesters used in the manufacture of fiber glass; the tertiary nitrogen provides a means of anchoring the polyester t0 the acidic glass fibers.

With polycarboxylic acids, such for example as adipic, terephthalic, phthalic, sebacic, and the like, my new dihydroxyalcohols form polyesters. These polyesters are characterized by the presence of tertiary nitrogens in their molecular make-up which makes them readily dyeable by acid dyes; it also improves the adhesion of rubber to fibers made from such polyesters.

The manner of carrying out my invention is described in the following specific examples. These examples are given by way of illustration only and are not intended as a limitation of my invention.

Example 1 .1,1-methylenebis 4- [3-(N-beta-hydr0xyethyl-4-piperidyl) propyl] piperidine no-cmcm-Qcmcmcm-Q-nom A solution of 63.5 grams of 1-(4-piperidyl)-3-(4-N- The procedure of Example 1 is repeated with the exception that I use l-(Z-piperidyl)-2-(Z-N-beta-hydroxyethylpiperidyl)ethane in place of the 1-(4-piperidyl)-3-(4-N- beta-hydroxyethylpiperidyl)propane.

Elxample 3.1,1'-ethylenebis 4- [3-(N-beta-hydroxyethyl- 4-piperidyl)propyl] piperidine Ho-cmom-@cmcmcaQ-mornn Into a two-liter flask equipped with a stirrer there are placed 127 grams of l-(4-piperidyl)-3-(4-N-beta-hydroxyethylpiperidyl) propane, 24.8 grams of ethylene chloride, 20 grams of sodium hydroxide, and one liter of Water. While stirring the reaction mixture, it is heated to about 85l00 C. As the heating continues, a reaction occurs and 1,1-ethylenebis 4-[3-(N-beta=hydroxyethyl-4-piperidyl)propyl] piperidine, which is formed, separates from the mixture as an oil. The heating and stirring are continued for about one-half hour. Then the mixture is cooled to room temperature. The reaction product which has crystallized is separated from the liquid by filtration. It is dried and recrystallized from benzene.

The so prepared 1,l'-ethylenebis 4-[3-(N-beta-hydroxyethyl-4-piperidyl)propyl] piperidine has a freezing point of about 111 C. It is insoluble in water but soluble in hot organic solvents, such as benzene.

s CHQCH CH O The procedure of Example 3 is repeated with the excepy y y p p y )p p in 200 l. of meth tion that I use l-(2-piperidyl)-3-(Z-N-beta-hydroxyethylnol is placed into a liter beaker equipped with a stirrer. The solution is stirred and 7.5 grams of a 53% solution piperidyl)propane in place of the 1-(4-piperidyl)-3-(4-N beta-hydroxyethylpiperidyl) propane.

thereby causing the reaction Example 5.1,I-tetramelhylenebis 4- [3-(N-betahydroxyelhyl-4-piperidyl)propyl] piperidine no mam-@cniomcuQ-mon4 The procedure of Example 3 is followed with the exception that 32 grams of 1,4-dichlor0butane is used in place [HOCH1CH1- @omomom-GEw] on. of the ethylene chloride. 2

Example 6.-] ,1 -ethylenebis 2- [3-(N-beta-hydr0xyethyl- The compound 2- iperidyl)propyl]-6-isopr0pylpiperidine 10 p [Ho-omom-moH1omoHr-](om):

S s CH: N CHsCHzCH N (J-H (CH2): 1 a

l S S HaOH 2 If CHzCHzCH If (CH2),

The procedure of Example 3 is repeated with the exception that 1-[2-(6-isopr0pyl)piperidyl]-3-(4-N-betahy- 20 droxyethylpiperidyl) propane is used in place of the 1-(4- piperidyl) -3- (4-N-beta-hydroxyethylpiperidyl propane.

I claim as my invention:

1. Methylenebis[(N hydroxyalkyl piperidyl)alkyl] piperidines whose formula is 25 HO CECE-Ii s s l 4. The compound CH: JHQOH 2 5. The compound R2 R1 (CHs)yz)X S S N- R )L (cm); H \+"'(GHZ)IF :J

References Cited UNITED STATES PATENTS 3,317,546 5/1967 Cislak et a1 260294 X WALTER A. MONDANCE, Primary Examiner. A. D. SPEVACK, Assistant Examiner. 

1. METHYLENEBIS((N- HYDROXYALKYL - PIPERIDYL)ALKYL) PIPERIDINES WHOSE FORMULA IS 